Liquid phase transmission electron microscopy (LP‐TEM) is a novel and highly promising technique for the in situ study of important nanoscale processes, in particular the synthesis and modification of various nanostructures in a liquid. Destabilization of the samples, including reduction, oxidation, or dissolution by interactions between electron beam, liquid, and sample, is still one of the main challenges of this technique. This work focuses on amorphous silica nanospheres and the phenomena behind their reshaping and dissolution in LP‐TEM. It is proposed that silica degradation is primarily the result of reducing radical formation in the liquid phase and the subsequent accelerated hydroxylation of the silica, while alterations in silica solid structure, pH, and oxidizing species formation had limited influence. Furthermore, the presence of water vapor instead of liquid water also results in degradation of silica. Most importantly however, it is shown that the addition of scavengers for reducing radicals significantly improved amorphous silica stability during LP‐TEM imaging. Devising such methods to overcome adverse effects in LP‐TEM is of the utmost importance for further development and implementation of this technique in studies of nanoscale processes in liquid.
Lignosulfonate was subjected to a reductive catalytic degradation in ethanol medium at 310 °C in the presence of alumina supported NiMo catalysts and H2. The liquid and solid products were analyzed with size exclusion chromatography (SEC), gas chromatography mass spectrometry (GC–MS), two-dimensional gas chromatography (GC × GC), heteronuclear single quantum coherence nuclear magnetic resonance (HSQC NMR) and elemental analysis. The highest oil yield and the lowest char yield obtained was 88 and 15 wt %, respectively. The liquefied species were mainly dimers and oligomers with minor yields of monomers. The catalyst was important for stabilization of reactive intermediates either by hydrogenation or coupling with ethanol. Simultaneous deoxygenation and desulfurization reactions took place in the presence of the catalyst; the oxygen and sulfur content in the oil fraction obtained after 4 h reaction time were 11.2 and 0.1 wt %, indicating considerable deoxygenation and desulfurization compared to the lignosulfonate feedstock (O, 30.8 wt %; S, 3.1 wt %). The effect of the reaction parameters such as temperature, reaction time and catalyst mass was studied. It was observed that by increasing the temperature from 260 to 310 °C the degradation increased, however, the SEC analysis showed that the degradation progressed only to a certain size range dimers to oligomers in the reaction temperatures studied. Investigating the effect of reaction time of 1, 2, 3, and 4 h indicated that degradation, deoxygenation, desulfurization and alkylation reactions progressed over time. The reusability of the catalyst without any pretreatment was confirmed by an almost constant oil yield in three repeated experiments with the same catalyst batch. The results show that alumina supported NiMo catalysts are very promising catalysts for conversion of lignosulfonate to liquid products.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.